Non-flak coated colouring pigment and method for the production and use thereof

ABSTRACT

The invention relates to a nonflake coated coloring pigment which consists of an inorganic or organic, amorphous or partially crystalline material and which is provided with at least one coating, where each layer comprises at least one cured melamine-formaldehyde resin or consists of one such resin. The pigment is particularly readily suitable for producing cosmetic products. It confers a pleasant skin sensation to the user of the cosmetic products.

The invention relates to a nonflake coated coloring pigment and to amethod for the production and use thereof. The invention also relates tocompositions which comprise such a pigment.

Cosmetic products often comprise pigments in order to give them acolored appearance. Some of these pigments convey to the user of thecosmetic products a harsh, dry and thus unpleasant sensation on theskin. This is the case particularly with pigments based on iron(III)hexacyanoferrate(II), which is also referred to as Prussian Blue, orchromium(III) oxide.

It is an object of the present invention to provide coloring pigments inparticular for cosmetic products and other products which are applied tothe skin which confer a pleasant sensation on the skin.

Surprisingly, it has been found that this object can be achieved bycoating the coloring pigments with a cured melamine-formaldehyde resin.

Coated pigments are known in principle. Thus, EP-A-0 601 378 describesflake mica pigments coated with melamine resin. These pigments are usedas effect pigments in metallic paints for automobiles, and the coatinghas the task of improving the storage stability of the paint and alsothe surface properties of the resulting paint film.

DE-A-197 10 619 discloses solids particles coated with melamine resinwhich are added to impregnating resin solutions for producing laminatesin order to improve the abrasion resistance of the wooden materialscoated with the laminates. The core of the coated solids particlesconsists of quartzes, nitrides, carbides. These are not coloringpigments.

The present invention provides a nonflake coated coloring pigment whichis characterized in that the pigment consists of an inorganic ororganic, amorphous or partially crystalline material which is providedwith at least one coating, where each layer comprises at least one curedmelamine-formaldehyde resin or consists of one such resin. Cosmeticproducts and other products which are applied to the skin confer to theuser a pleasant sensation on the skin if they comprise a coloringpigment according to the invention.

The pigment is advantageously iron(III) hexacyanoferrate(II) orchromium(III) oxide. However, it is also possible to coat other pigmentsin the same way with a cured melamine-formaldehyde resin. These are, forexample, titanium(IV) oxide, zirconium(IV) oxide, and oxides of iron,such as magnetite and hematite.

With the crosslinked melamine-formaldehyde resins, some of the melaminemolecules can also be replaced by other crosslinkable molecules, suchas, for example, phenols, guanamines or urea. The melamine-formaldehyderesins can be unetherified or etherified melamine-formaldehyde adducts,for example alkoxymethylol-melamines with C₁-C₆-alkoxy groups, such asmethoxy or n-butoxy groups, and precondensates. By way of an example, anunetherified resin is Madurit MW 909, or an etherified resin is MaduritSMW 818 (both products from Solutia, Wiesbaden, Germany). Some of themelamine-formaldehyde resin can also be replaced by other crosslinkingorganic polymers. Of suitability here are in particular those whichlikewise have a high refractive index, very particularly those whichhave a refractive index which is greater than that of the uncoatedpigment.

As a result of coating the pigment with melamine-formaldehyde withoutthe addition of dye, the intrinsic color of the pigment also changesdepending on the coating thickness. As the thickness of the coatingincreases, the color impression shifts in the direction of lighter andpaler colors. At the coating thicknesses necessary for a more pleasantsensation on the skin, however, the effect of lightening is barelyperceptible to the eye. The lightening naturally does not apply tocolorless pigments, such as, for example, titanium(IV) oxide orzirconium(IV) oxide.

In contrast to flake pigments, upon coating with melamine-formaldehydeno interference color which can be adjusted through the coatingthickness is formed. The reason for this is essentially the very unevensurface with nonflake pigments, which prevents a uniform layer thicknessfor forming an interference.

Any organic and inorganic dyes and also if appropriate colorless UVabsorbers can be incorporated into the melamine-formaldehyde resins. Adecisive factor for incorporation into the polymer matrix here is onlyits solubility in the medium in which the coating reaction is carriedout. Even water-soluble dyes, such as, for example, eosine, fluorosceinor Victoria Pure Blue BO can be embedded into the polymer matrix withoutsubsequently bleeding. In the case of lipophilic dyes, the coatingreaction can likewise be carried out in an aqueous medium if thesolubility promoters customary to the average skilled worker in thefield are added. One example of a solubility promoter which may bementioned here is 1-methyl-2-pyrrolidone.

In order to obtain color nuances it is possible to use the customaryprinciples of additive color mixtures. Here, the color shades can beadjusted by mixing the dyes beforehand and introducing them togetherinto a polymer layer, or by applying two or more dye-polymer layers tothe inorganic substrate one after the other so that layers of differentcolor are superimposed.

Acidochromic dyes, i.e. dyes whose color depends on the pH, can alsoessentially be incorporated into the melamine-formaldehyde resin whileretaining the color shade and color change point. Examples which may begiven here are phenolphthalein, bromothymol blue, bromoxylene blue andthymolphthalein.

Besides the fluoroscein already mentioned above, other fluorescent dyes,optical brighteners or other UV light-absorbing dyes can be incorporatedinto the polymer matrix.

In particular, it is advisable to incorporate two or more dyes, at leastone dye of which is a fluorescent dye. It is particularly advantageousto incorporate at least two fluorescent dyes, the second fluorescent dyebeing added in considerably smaller amounts. As a result, pigments canbe obtained whose resulting fluorescent color differs significantly fromthe fluorescent color of the starting materials. In this way, it ispossible to synthesize a large number of differently fluorescentpigments in a simple way. By varying the type of the fluorescent dye ordyes and varying the second dye added in considerably smaller amounts,both with regard to the type and also the concentration, it is possibleto produce a large bandwidth of fluorescent colors. Often, as a resultof the low content of color-determining dyes, in visible light thesepigments have a very inconspicuous and comparatively pale effect.Besides the base colors red, green and blue, well in excess of onehundred different fluorescent colors which can be clearly differentiatedby eye can be realized.

By depositing a polymer layer comprising one or more fluorescent dyesonto a polymer layer which already comprises previously applied dye, itis possible to significantly increase the brilliance and luminance ofthe pigments. Moreover, bleaching of the underlying layers can besuppressed by the absorption of UV light. Such UV protection can also beachieved by incorporating UV absorbers into the dye-containing polymerlayer itself.

In principle, suitable UV absorbers are all UV filters. Of particularpreference are those UV filters whose physiological acceptability hasbeen demonstrated. Both for UV-A filters and also for UV-B filters thereare many tried and tested substances known from the specialistliterature. Examples here are benzylidenecamphor derivatives, such as3-(4′-methylbenzylidene)-dl-camphor, 3-benzylidenecamphor, polymers ofN-{(2 and 4)-[(2-oxoborn-3-ylidene)methyl]benzyl}acrylamide,N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)anilinium methylsulfate orα-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid, benzoyl- ordibenzoylmethane, such as, for example,1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione or4-isopropyldibenzoylmethane, benzophenones, such as, for example,2-hydroxy-4-methoxybenzophenone or2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the sodium saltthereof, methoxycinnamic esters, such as, for example, octylmethoxycinnamate, isopentyl 4-methoxycinnamate and the isomer mixturethereof, salicylate derivatives, such as, for example, 2-ethylhexylsalicylate, 4-isopropylbenzyl salicylate or 3,3,5-trimethylcyclohexylsalicylate, 4-aminobenzoic acid and derivatives thereof, such as2-ethylhexyl 4-(dimethylamino)benzoate or ethoxylated ethyl4-aminobenzoate, and further substances, such as, for example,2-ethylhexyl 2-cyano-3,3-diphenylacrylate,2-phenylbenzimidazole-5-sulfonic acid, and the potassium, sodium andtriethanolamine salts thereof,3,3′-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethanesulfonicacid and salts thereof and2,4,6-trianilino(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine.

Further suitable organic UV filters are, for example,2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)-propyl)phenol,bis(2-ethylhexyl)4,4′-[(6-[4-((1,1-di-methylethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bisbenzoate,α-(trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl[and about 6%methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] andabout 1.5% methyl[3-[p-[2,2-bis-(ethoxycarbonyl)vinyl)phenoxy)propenyl)and 0.1 to 0.4% (methylhydrogen]silylene]] (n≈60) (CAS No. 207574-74-1),2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol),2,2′-(1,4-phenylene)bis(1H-benzimidazole-4,6-disulfonic acid, monosodiumsalt) and2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.

Preferred compounds with UV-absorbing properties are3-(4′-methylbenzylidene)-dl-camphor,1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione,4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octylmethoxycinnamate, 3,3,5-trimethyl cyclohexylsalicylate, 2-ethylhexyl4-(dimethylamino)-benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,2-phenylbenzimidazole-5-sulfonic acid, and the potassium, sodium, andtriethanolamine salts thereof.

By combining two or more UV filters, the protective effect againstharmful influences of UV radiation can be optimized.

The coated coloring pigments can be produced by depositing crosslinkingmelamine-formaldehyde resins onto the suspended pigments andsubsequently curing them, i.e. crosslinking the melamine-formaldehyderesins.

The method according to the invention for producing a coloring pigmentwith one or more coatings involves, in the case of a single coating,

-   a first step in which a coloring pigment is suspended in a basic    aqueous medium comprising melamine and formaldehyde and/or    methylolmelamine, which may optionally be alkoxylated, and-   a second step in which crosslinking of the organic constituents is    brought about by lowering the pH into the acidic range,    and in the case of a multiple coating the first and second step is    repeated with the product of the preceding coating operation.

It has been found that it is particularly advantageous to reduce the pHin the second process step by adding hydrogen peroxide, by oxidizingexcess or unreacted formaldehyde from the first process step to giveformic acid. Since formaldehyde is problematical in cosmeticapplications, a pigment can thus be provided which is free from freeformaldehyde molecules and thus cosmetically acceptable. This alsofunctions with methylolmelamines since these in most cases also comprisesufficient amounts of free formaldehyde.

In the method according to the invention, some of the melamine can bereplaced by other crosslinking molecules from the group consisting of“guanamines, phenols and ureas” and/or some of the methylolmelamine canbe replaced by corresponding guanamine, phenol or urea analogs.

Inorganic or organic dyes and/or inorganic or organic UV absorbers canbe added prior to the onset of the crosslinking reaction or during thecrosslinking reaction.

Should the dyes or UV absorbers not completely dissolve in the aqueousmedium, then complete dissolution can be brought about using solubilitypromoters. This applies particularly when using lipophilic substances.

The layer thickness of the coating can be controlled through themelamine-formaldehyde resin concentration. For example, at highconcentrations, greater layer thicknesses are obtained than at lowconcentrations. The pH is also a suitable means for controlling thelayer thickness. Low pH values lead to thinner coatings. DE 1595386describes, moreover, the controlling of layer thicknesses through theaddition of protective colloids.

Preferred overall layer thicknesses of substrates with one or morecoatings are preferably 0.2 μm to 4 μm.

By using excess melamine-formaldehyde resin, additional and essentiallyround melamine-formaldehyde resin particles which, besides organic dyes,can also comprise UV absorbers or are entirely free from dyes or UVabsorbers can be deposited onto the outermost coating.

Depending on the reaction procedure it is possible to control the numberof spheres per coloring pigment particle, the sphere diameter, and thedistribution of the sphere diameter (dispersity). For cosmetic purposesin particular, a certain content of spheres is advantageous for animproved sensation on the skin.

An excessively high content of spheres, however, reduces the brillianceand the appearance of the pigment. If the content of dye is sufficient,the additional spheres have a color which matches the coloring pigments.

The space-time yield relevant from the point of view of costeffectiveness can be significantly increased by adding polymers withstrongly acidic groups, as is described, for example, in EP 0415273.

For certain applications it may be advantageous to also incorporate intothe condensation product of the outermost layer of the polymerfunctional groups other than the specified strongly acidic groups inorder to improve these, for example with regard to their bindercompatibility and the dispersion behavior. Subsequently providing theoutermost layer of the crosslinked organic polymer with functionalgroups by subsequent reaction of the melamine-formaldehyde resins isalso possible. DD 224 602 describes various ways of functionalizingresins.

Functional groups for the purposes of this invention may be anyhydrophilic or hydrophobic, acidic or basic groups, thus including, forexample, even purely hydro-phobic largely inert groups, such as, forexample, alcyl groups.

According to a method described in DD 224 602, the functional groups areincorporated into the surface of the polymer particles by carrying outthe polycondensation reaction of the melamine-formaldehyde resin in thepresence of amino functional compounds, where the amino functionalcompounds carry further functional groups besides the amino group. Theamino functional compounds are added in amounts of from preferably 2 to20 mol percent, based on the amount of methylolmelamine used, andincorporated into the melamine-formaldehyde network via the aminofunction. Thus, it is possible, for example when using amino acids, toincorporate carboxyl groups, or in the case of the sulfobetaines oraminophosphonic acids, to incorporate sulfo- or phosphonic acid groupsinto the surface of the particles. Such —COOH, —SO₃H and —PO₂H groupscan in turn be reacted with other compounds. For example, the acidgroups can be converted, by reaction with thionyl chloride, intocorresponding acid chlorides which, for example, can in turn be reactedwith alcohols or amines, forming the corresponding esters or amides.This method of surface modification is characterized by its simplicitysince in an only slightly modified condensation process,functionalization of the melamine-formaldehyde resin surface takes placedirectly. However, disadvantageous effects which may arise are that, asa result of the condensation process, the corresponding functionalitiesare also incorporated in the polymer volume and thus the adhesion to theunderlying layers or, in the case of a single-layer structure, theadhesion to the substrate, may be reduced. On the other hand, however,in the case of an appropriate selection for certain systems, theadhesion to the underlying layers or to the substrate can be increasedif, as a result of the surface modification agent, groups are introducedwhich both improve the compatibility to the surrounding medium and alsoimpart adhesion to the underlying layers or the substrate. In thismethod, however, as a result of the incorporation into themelamine-formaldehyde network, relatively large amounts of thesurface-functionalizing agent are required. Also, more complex chemicalfunctionalities through simple incorporation during polycondensation canbe obtained only with difficulty.

Another method of surface functionalization starts therefore from analready polycondensed melamine-formaldehyde surface which has free,uncrosslinked methylolamine (NH—CH₂OH) or amino groups. These groupscan, for example, be reacted with carbonoyl chlorides in a simple way.Thus, for example in the case of the use of long-chain carbonoylchlorides, hydrophobicization of the pigment can be achieved. Withperfluorinated acid chlorides, such as, for example, perfluorooctanoicacid, both hydrophobic and also lipophobic surfaces can be obtained. Byusing complex acid chlorides, which may comprise, for example, stronglyUV light-absorbing groups, the melamine-formaldehyde surface can alsocontain further-reaching functionalities, e.g. a UV protection.

Advantageous embodiments of the invention arise from the dependentclaims.

The invention also relates to compositions and cosmetic preparationswhich comprise one or more of the nonflake coated carrier materials ascoloring pigment.

The nonflake coated coloring pigments according to the invention in thecompositions or preparations can of course also be combined with anytype of cosmetic raw materials and auxiliaries. These include, interalia, oils, fats, waxes, film formers, preservatives and auxiliarieswhich generally determine application properties, such as, for example,thickeners and rheological additives, such as, for example, bentonites,hectorites, silicon dioxides, Ca silicates, gelatins, high molecularweight carbohydrates and/or surface-active auxiliaries, etc.

The formulations comprising the coloring pigments according to theinvention can belong to the lipophilic, hydrophilic or hydrophobic type.In the case of heterogeneous formulations with discrete aqueous andnonaqueous phases, the coloring pigments according to the invention mayin each case be present in only one of the two phases, or else bedistributed over both phases.

The ph values of the formulations can be between 1 and 14, preferablybetween 2 and 11 and particularly preferably between 5 and 8.

The concentrations of the coloring pigments according to the inventionin the formulation are not restricted. Depending on the applicationcase, they can be between 0.001 (rinse-off products, e.g. shower gels)and 100% (e.g. shine-effect articles for particular applications).

Furthermore, the coloring pigments according to the invention can alsobe combined with cosmetic active ingredients. Suitable activeingredients are, for example, insect repellants, UV A/BC protectivefilters (e.g. OMC, B3, MBC), anti-aging active ingredients, vitamins andderivatives thereof (e.g. vitamin A, C, E, etc.), self-tanning agents(e.g. DHA, erytrolose, etc.) and further cosmetic active ingredients,such as, for example, bisabolol, LPO, ectoin, emblica, allantoin,bioflavanoids and derivatives thereof.

The preparations here are usually preparations which can be appliedtopically, for example cosmetic or dermatological formulations. In thiscase, the preparations comprise a cosmetically or dermatologicallysuitable carrier and optionally further suitable ingredients dependingon the desired profile of properties.

As stated above, preparations which are particularly preferred accordingto the invention preferably comprise UV-B and UV-A-I filters. Inprinciple, all UV filters are suitable for a combination with thecoloring pigments according to the invention. Particular preference isgiven to those UV filters whose physiological acceptability has alreadybeen demonstrated. Both for UVA and also UVB filters there are manytried and tested substances known from the specialist literature, e.g.

-   benzylidinecamphor derivatives, such as    3-(4′-methyl-benzylidene)-dl-camphor (e.g. Eusolex® 6300),    3-benzylidenecamphor (e.g. Mexoryl® SD), polymers of N-{(2 and    4)-[(2-oxoborn-3-ylidene)methyl]benzyl}-acrylamide (e.g. Mexoryl®    SW), N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)anilinium    methylsulfate (e.g. Mexoryl® SK) or    (2-oxoborn-3-ylidene)toluene-4-sulfonic acid (e.g. Mexoryl® SL),-   benzoyl or dibenzoylmethanes, such as    1-(4-tert-butyl-phenyl)-3-(4-methoxyphenyl)propane-1,3-dione (e.g.    Eusolex® 9020) or 4-isopropyldibenzoylmethane (e.g. Eusolex® 8020),-   benzophenones, such as 2-hydroxy-4-methoxybenzophenone (e.g.    Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid    and its sodium salt (e.g. Uvinul® MS-40),-   methoxycinnamic esters, such as octyl methoxycinnamate (e.g.    Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of    the isomers (e.g. Neo Heliopan® E 1000),-   salicylate derivatives, such as 2-ethylhexyl salicylate (e.g.    Eusolex® OS), 4-isopropylbenzyl salicylate (e.g. Megasol®) or    3,3,5-trimethylcyclohexyl salicylate (e.g. Eusolex® HMS),-   4-aminobenzoic acid and derivatives, such as 4-amino-benzoic acid,    2-ethylhexyl 4-(dimethylamino)benzoate (e.g. Eusolex® 6007),    ethoxylated ethyl 4-aminobenzoate (e.g. Uvinul® P25),-   phenylbenzimidazolesulfonic acids, such as    2-phenyl-benzimidazole-5-sulfonic acid, and its potassium, sodium    and triethanolamine salts (e.g. Eusolex® 232),    2,2-(1,4-phenylene)bisbenzimidazole-4,6-disulfonic acid or salts    thereof (e.g. Neoheliopan® AP) or    2,2-(1,4-phenylene)bisbenzimidazole-6-sulfonic acid;    and further substances, such as-   2-ethylhexyl 2-cyano-3,3-diphenylacrylate (e.g. Eusolex® OCR),-   3,3′-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethanesulfonic    acid, and its salts (e.g. Mexoryl® SX) and-   2,4,6-trianilino(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine (e.g.    Uvinul® T 150)-   hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (e.g. Uvinul® UVA    Plus, BASF).

The compounds given in the list should only be regarded as examples. Itis of course also possible to use other UV filters.

These organic UV filters are generally incorporated into cosmeticformulations in an amount of from 0.5 to 10 percent by weight,preferably 1-8%.

Further suitable organic UV filters are, for example,

-   2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol    (e.g. Silatrizole®),-   bis(2-ethylhexyl)    4,4′-[(6-[4-((1,1-dimethyl-ethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bisbenzoate    (e.g. Uvasorb® HEB),-   α-(trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy-(dimethyl[and    about 6%    methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl]    and about 1.5%    methyl[3-[p-[2,2-bis(ethoxy-carbonyl)vinyl)phenoxy)propenyl) and 0.1    to 0.4% (methylhydrogen]silylene]] (n≈60) (CAS No. 207 574-74-1),-   2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)    (CAS No. 103 597-45-1),-   2,2′-(1,4-phenylene)bis(1H-benzimidazole-4,6-disulfonic acid,    monosodium salt) (CAS no. 180 898-37-7) and-   2,4-bis{[4-(2-ethylhexylbxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine    (CAS No. 103 597-45-, 187 393-00-6),-   bis(2-ethylhexyl)    4,4′-[(6-[4-((1,1-dimethyl-ethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bisbenzoate    (e.g. Uvasorb® HEB).

Organic UV filters are gene-rally incorporated into cosmeticformulations in an amount of from 0.5 to 20 percent by weight,preferably 1-15%.

Conceivable inorganic UV filters are those from the group of titaniumdioxides, such as, for example, coated titanium dioxide (e.g. Eusolex®T-2000, Eusolex® T-AQUA), zinc oxides (e.g. Sachtotec®), iron oxides andalso cerium oxides. These inorganic UV filters are generallyincorporated into cosmetic preparations in an amount of from 0.5 to 20percent by weight, preferably 2-10%.

Preferred compounds with UV-filtering properties are3-(4′-methylbenzylidene)-dl-camphor,1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione,4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octylmethoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl4-(dimethylamino)-benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,2-phenylbenzimidazole-5-sulfonic acid, and its potassium, sodium andtriethanolamine salts.

Optimized compositions can comprise, for example, the combination of theorganic UV filter 4′-methoxy-6-hydroxyflavone with1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione and3-(4′-methyl-benzylidene)-dl-camphor. This combination gives broadbandprotection, which can be further supplemented by adding inorganic UVfilters, such as titanium dioxide microparticles.

All of the specified UV filters can also be used in encapsulated form.In particular, it is advantageous to use organic UV filters inencapsulated form. Specifically, the following advantages arise:

-   -   The hydrophilicity of the capsule wall can be adjusted        irrespective of the solubility of the UV filter. Thus, for        example, even hydrophobic UV filters can be incorporated into        purely aqueous preparations. In addition, the oily impression        upon applying the hydrophobic preparation comprising UV filters        which is often regarded as being unpleasant is prevented.    -   Certain UV filters, in particular dibenzoylmethane derivatives,        exhibit only reduced photostability in cosmetic preparations. By        encapsulating these filters or compounds which impair the        photo-stability of these filters, such as, for example, cinnamic        acid derivatives, it is possible to increase the photostability        of the overall preparation.    -   In the literature, the skin penetration by organic UV filters        and the irritancy potential associated therewith upon direct        application to the human skin is discussed time and again. By        encapsulating the corresponding substances as proposed here,        this effect is prevented.    -   In general, by encapsulating individual UV filters or other        ingredients, preparation problems which arise as a result of        individual preparation constituents interacting with one        another, such as crystallization processes, precipitations and        agglomeration, can be avoided since interaction is prevented.

Suitable capsules can have walls made of inorganic or organic polymers.For example, U.S. Pat. No. 6,242,099 B1 describes the production ofsuitable capsules with walls made of chitin, chitin derivatives orpoly-hydroxylated polyamines. Capsules to be used particularlypreferably according to the invention have walls which can be obtainedby a sol-gel process as described in the applications WO 00/09652, WO00/72806 and WO 00/71084. Preference is given here in turn to capsuleswhose walls are constructed from silica gel (silica; undefined siliconoxide hydroxide). The production of corresponding capsules is known tothe person skilled in the art, for example from the cited patentapplications, the contents of which expressly also belong to thesubject-matter of the present application.

Here, the capsules are present in preparations according to theinvention preferably in amounts which ensure that the encapsulated UVfilters are present in the preparation in the amounts stated above.

A protective effect against oxidative stress and against the effect offree radicals can be achieved if the preparations comprise one or moreantioxidants.

There are many tried and tested substances known from the specialistliterature which can be used as anti-oxidants, e.g. amino acids (e.g.glycine, histidine, tyrosine, tryptophan) and derivatives thereof,imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, suchas D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g.anserine), carotinoids, carotenes (e.g. α-carotene, β-carotene,lycopene) and derivatives thereof, chlorogenic acid and derivativesthereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid),aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin,glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,γ-linoleyl, cholesteryl and glyceryl esters thereof), and salts thereof,dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionicacid and derivatives thereof (esters, ethers, peptides, lipids,nucleotides, nucleosides and salts), and sulfoximine compounds (e.g.buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones,penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses(e.g. pmol to μmol/kg), and also (metal) chelating agents (e.g.α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin),α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid,bile acid, bile extract, bilirubin, biliverdin, EDTA, EGTA andderivatives thereof, unsaturated fatty acids and derivatives thereof,vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbylphosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitaminE acetate), vitamin A and derivatives (e.g. vitamin A palmitate), andconiferyl benzoate of benzoin resin, rutinic acid and derivativesthereof, α-glycosylrutin, ferulic acid, furfurylideneglucitol,carnosine, butylhydroxytoluene, butylhydroxyanisole,nordohydroguaiaretic acid, tri-hydroxybutyrophenone, quercitin, uricacid and derivatives thereof, mannose and derivatives thereof, zinc andderivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof(e.g. seleno-methionine), stilbenes and derivatives thereof (e.g.stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are likewise suitable for use in the cosmeticpreparations according to the invention. Known and commercial mixturesare, for example, mixtures comprising, as active ingredients, lecithin,L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex® AP), naturaltocopherols, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citricacid (e.g. Oxynex® K LIQUID), tocopherol extracts from natural sources,L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g.Oxynex® L LIQUID), DL-α-tocopherol, L-(+)-ascorbyl palmitate, citricacid and lecithin (e.g. Oxynex® LM) or butylhydroxytoluene (BHT),L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex® 2004). Suchantioxidants are used with the coloring pigments according to theinvention in such compositions usually in ratios in the range from1000:1 to 1:1000, preferably in amounts of from 100:1 to 1:100.

As further ingredients, the preparations according to the invention cancomprise vitamins. Preferably, vitamins and vitamin derivatives chosenfrom vitamin A, vitamin A propionate, vitamin A palmitate, vitamin Aacetate, retinol, vitamin B, thiamine chloride hydrochloride (vitaminB₁), riboflavin (vitamin B₂), nicotinamide, vitamin C (ascorbic acid),vitamin D, ergocalciferol (vitamin D₂), vitamin E, DL-α-tocopherol,tocopherol-E-acetate, tocopherol hydrogensuccinate, vitamin K₁, esculin(vitamin P active ingredient), thiamine (vitamin B₁), nicotinic acid(niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B₆), pantothenicacid, biotin, folic acid and cobalamine (vitamin B₁₂) are present in thecosmetic preparations according to the invention, particularlypreferably vitamin A palmitate, vitamin C, DL-α-tocopherol,tocopherol-E-acetate, nicotinic acid, pantothenic acid and biotin.Vitamins are used here with the coloring pigments according to theinvention usually in ratios in the range from 1000:1 to 1:1000,preferably in amounts of from 100:1 to 1:100.

Moreover, the preparations according to the invention can comprisefurther customary skin-gentle or skincare active ingredients. These canin principle be all active ingredients known to the person skilled inthe art.

Particularly preferred active ingredients are pyrimidinecarboxylic acidsand/or aryl oximes.

Pyrimidinecarboxylic acids are present in halophilic microorganisms andplay a role in the osmoregulation of these organisms (E. A. Galinski etal., Eur. J. Biochem., 149 (1985) pages 135-139). Here, among thepyrimidinecarboxylic acids, mention is made in particular of ectoin((S)-1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) andhydroxyectoin((S,S)-1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidine-carboxylicacid) and derivatives thereof. These compounds stabilize enzymes andother biomolecules in aqueous solutions and organic solvents. Inaddition, they stabilize enzymes in particular against denaturingconditions, such as salts, extreme pH values, surfactants, urea,guanidinium chloride and other compounds.

Ectoin and ectoin derivatives, such as hydroxyectoin, can advantageouslybe used in medicaments. In particular, hydroxyectoin can be used forproducing a medicament for the treatment of skin disorders. Other fieldsof use of hydroxyectoin and other ectoin derivatives are typically infields where, for example, trehalose is used as additive. Thus, ectoinderivatives, such as hydroxyectoin, can be used as protectant in driedyeast and bacteria cells. Pharmaceutical products, such asnon-glycosylated pharmaceutically effective peptides and proteins, e.g.t-PA can also be protected with ectoin or its derivatives.

Among the cosmetic applications, the use of ectoin and ectoinderivatives for the care of aged, dry or irritated skin is mentioned inparticular. Thus, European patent application EP-A-0 671 161 describesin particular that ectoin and hydroxyectoin are used in cosmeticpreparations such as powders, soaps, surfactant-containing cleansingproducts, lipsticks, blusher, make-ups, care creams and sunscreenpreparations.

Here, preference is given to using a pyrimidine-carboxylic acidaccording to formula I below,

in which R¹ is a radical H or C1-8-alkyl, R² is a radical H orC₁₋₄-alkyl and R³, R⁴, R⁵ and R⁶, in each case independently of oneanother, are a radical from the group H, OH, NH₂ and C1-4-alkyl.Preference is given to using pyrimidinecarboxylic acids in which R² is amethyl or an ethyl group, and R¹ or R⁵ and R⁶ are H. Particularpreference is given to using the pyrimidinecarboxylic acids ectoin((S)-1,4,5,6-tetra-hydro-2-methyl-4-pyrimidinecarboxylic acid) andhydroxyectoin((S,S)-1,4,5,6-tetrahydro-5-hydroxy-2-methyl-4-pyrimidinecarboxylicacid). Here, the preparations according to the invention comprisepyrimidinecarboxylic acids of this type preferably in amounts up to 15%by weight. Preferably, the pyrimidinecarboxylic acids are used here inratios of from 100:1 to 1:100 relative to the coloring pigmentsaccording to the invention, particular preference being given to ratiosin the range 1:10 to 10:1.

Among the aryl oximes, preference is given to using2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO,LPO or F5. Its suitability for use in cosmetic compositions is known,for example, from the German laid-open specification DE-A-41 16 123.Preparations which comprise 2-hydroxy-5-methyllaurophenone oxime areaccordingly suitable for treating skin disorders which involveinflammations. It is known that such preparations can be used, forexample, for the treatment of psoriasis, various forms of eczema,irritative and toxic dermatitis, UV dermatitis and further allergicand/or inflammatory disorders of the skin and of the skin appendages.Preparations according to the invention which, besides the coloringpigments according to the invention, additionally comprise an aryloxime, preferably 2-hydroxy-5-methyllaurophenone oxime, exhibitsurprising anti-inflammatory suitability. Here, the preparationspreferably comprise 0.01 to 10% by weight of the aryl oxime, it beingparticularly preferred for the preparation to comprise 0.05 to 5% byweight of aryl oxime.

All compounds or components which can be used in the preparations areeither known or available commercially or can be synthesized by knownmethods.

The coloring pigments according to the invention can be incorporatedinto cosmetic preparations in the customary manner. Preparations forexternal application, for example in the form of cream, lotion, gel orsolution which can be sprayed onto the skin are suitable. For internalapplication, administration forms such as capsules, sugar-coatedtablets, powders, tablet solutions or solutions are suitable.

Examples of application forms of the compositions or preparationsaccording to the invention which may be mentioned are: solutions,suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams,lotions, powders, soaps, surfactant-containing cleansing preparations,oils, aerosols and sprays. Further application forms are, for example,sticks, shampoos and shower baths. Any customary carrier substances,auxiliaries and optionally further active ingredients can be added tothe preparation.

Preferred auxiliaries originate from the group of preservatives,antioxidants, stabilizers, solubility promoters, vitamins, colorants,odor improvers.

Ointments, pastes, creams and gels can comprise the customary carriersubstances, e.g. animal and vegetable fats, waxes, paraffins, starch,tragacanth, cellulose derivatives, polyethylene glycols, silicones,bentonites, silica, talc and zinc oxide or mixtures of these substances.

Powders and sprays can comprise the customary carrier substances, e.g.milk sugar, talc, silica, aluminum hydroxide, calcium silicate andpolyamide powder or mixtures of these substances. Sprays canadditionally comprise the customary propellants, e.g.chlorofluorocarbons, propane/butane or dimethyl ether.

Solutions and emulsions can comprise the customary carrier substances,such as solvents, solubility promoters and emulsifiers, e.g. water,ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol,benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particularcotton seed oil, peanut oil, corn oil, olive oil, castor oil and sesameoil, glycerol fatty acid esters, polyethylene glycols and fatty acidesters of sorbitan or mixtures of these substances.

Suspensions can comprise the customary carrier substances, such asliquid diluents, e.g. water, ethanol or propylene glycol, suspendingagents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitolesters and polyoxyethylene sorbitan esters, microcrystalline cellulose,aluminum metahydroxide, bentonite, agar agar and tragacanth or mixturesof these substances.

Soaps can comprise the customary carrier substances, such as alkalimetal salts of fatty acids, salts of fatty acid half-esters, fatty acidprotein hydrolysates, isothionates, lanolin, fatty alcohol, vegetableoils, plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleansing products can comprise the customarycarrier substances, such as salts of fatty alcohol sulfates, fattyalcohol ether sulfates, sulfosuccinic half-esters, fatty acid proteinhydrolysates, isothionates, imidazolinium derivatives, methyl taurates,sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fattyalcohols, fatty acid glycerides, fatty acid diethanolamides, vegetableand synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acidesters or mixtures of these substances.

Face and body oils can comprise the customary carrier substances such assynthetic oils, such as fatty acid esters, fatty alcohols, siliconeoils, natural oils, such as vegetable oils and oily plant extracts,paraffin oils, lanolin oils or mixtures of these substances.

Further typical cosmetic application forms are also lipsticks, lipcaresticks, mascara, eyeliner, eye shadows, blusher, powder, emulsion andwax make-up, and sunscreen, presun and after-sun preparations.

Preferred preparation forms according to the invention include, inparticular, emulsions.

Emulsions according to the invention are advantageous and comprise, forexample, the specified fats, oils, waxes and other fatty substances, andalso water and an emulsifier, as is customarily used for such a type ofpreparation.

The lipid phase can advantageously be chosen from the following group ofsubstances:

-   -   mineral oils, mineral waxes    -   oils, such as triglycerides of capric acid or of caprylic acid,        and also natural oils, such as, for example, castor oil;    -   fats, waxes and other natural and synthetic fatty substances,        preferably esters of fatty acids with alcohols of low carbon        number, e.g. with isopropanol, propylene glycol or glycerol, or        esters of fatty alcohols with alkanoic acids of low carbon        number or with fatty acids;    -   silicone oils, such as dimethylpolysiloxanes,        diethylpolysiloxanes, diphenylpolysiloxanes, and mixed forms        thereof.

The oil phase of the emulsions, oleogels and hydro-dispersions orlipodispersions for the purposes of the present invention isadvantageously chosen from the group of esters of saturated and/orunsaturated, branched and/or unbranched alkanecarboxylic acids of chainlength from 3 to 30 carbon atoms and saturated and/or unsaturated,branched and/or unbranched alcohols of chain length from 3 to 30 carbonatoms, from the group of esters of aromatic carboxylic acids andsaturated and/or unsaturated, branched and/or unbranched alcohols ofchain length from 3 to 30 carbon atoms. Such ester oils can thenadvantageously be chosen from the group consisting of isopropylmyristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate,n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate,isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate,2-ethylhexyl laurate, 2-hexaldecyl stearate, 2-octyldodecyl palmitate,oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate andsynthetic, semisynthetic and natural mixtures of such esters, e.g.jojoba oil.

In addition, the oil phase can be chosen advantageously from the groupof branched and unbranched hydrocarbons and hydrocarbon waxes, siliconeoils, dialkyl ethers, the group of saturated or unsaturated, branched orunbranched alcohols, and fatty acid triglycerides, namely thetriglyceryl esters of saturated and/or unsaturated, branched and/orunbranched alkane-carboxylic acids of chain length from 8 to 24, inparticular 12-18, carbon atoms. The fatty acid triglycerides can, forexample, be chosen advantageously from the group of synthetic,semi-synthetic and natural oils, e.g. olive oil, sunflower oil, soyaoil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palmkernel oil and the like.

Any mixtures of such oil and wax components are also to be usedadvantageously for the purposes of the present invention. It may in someinstances also be advantageous to use waxes, for example cetylpalmitate, as the sole lipid component of the oil phase.

Advantageously, the oil phase is chosen from the group consisting of2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate,isoeicosane, 2-ethylhexyl cocoate, C₁₂₋₁₅-alkyl benzoate,caprylic-capric triglyceride, dicapryl ether.

Mixtures of C₁₂₋₁₅-alkyl benzoate and 2-ethylhexyl isostearate, mixturesof C₁₂₋₁₅-alkyl benzoate and isotridecyl isononanoate, and mixtures ofC₁₂₋₁₅-alkyl benzoate, 2-ethylhexyl isostearate and isotridecylisononanoate are particularly advantageous.

Of the hydrocarbons, paraffin oil, squalane and squalene are to be usedadvantageously for the purposes of the present invention.

Furthermore, the oil phase can also advantageously have a content ofcyclic or linear silicone oils or consist entirely of such oils,although it is preferred to use an additional content of other oil phasecomponents apart from the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used assilicone oil to be used according to the invention. However, othersilicone oils can also be used advantageously for the purposes of thepresent invention, for example hexamethylcyclo-trisiloxane,polydimethylsiloxane, poly(methylphenyl-siloxane).

Also particularly advantageous are mixtures of cyclo-methicone andisotridecyl isononanoate, and of cyclo-methicone and 2-ethylhexylisostearate.

The aqueous phase of the preparations according to the inventionoptionally advantageously comprises alcohols, diols or polyols of lowcarbon number, and ethers thereof, preferably ethanol, isopropanol,propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethylor monobutyl ether, propylene glycol monomethyl, monoethyl or monobutylether, diethylene glycol monomethyl or monoethyl ether and analogousproducts, and also alcohols of low carbon number, e.g. ethanol,isopropanol, 1,2-propanediol, glycerol and in particular one or morethickeners, which can be chosen advantageously from the group consistingof silicon dioxide, aluminum silicates, polysaccharides and derivativesthereof, e.g. hyaluronic acid, xanthan gum,hydroxypropylmethylcellulose, particularly advantageously from the groupof polyacrylates, preferably a polyacrylate from the group of so-calledcarbopols, for example carbopol grades 980, 981, 1382, 2984, 5984, ineach case individually or in combination.

In particular, mixtures of the abovementioned solvents are used. In thecase of alcoholic solvents, water may be a further constituent.

Emulsions according to the invention are advantageous and comprise, forexample, the specified fats, oils, waxes and other fatty substances, andalso water and an emulsifier, as is customarily used for such a type offormulation.

In a preferred embodiment, the preparations according to the inventioncomprise hydrophilic surfactants.

The hydrophilic surfactants are preferably chosen from the group ofalkyl glucosides, acyl lactylates, betaines and cocoamphoacetates.

The alkyl glucosides are for their part advantageously chosen from thegroup of alkyl glucosides which are characterized by the structuralformula

where R is a branched or unbranched alkyl radical having 4 to 24 carbonatoms and where {overscore (DP)} is an average degree of glucosylationof up to 2.

The value {overscore (DP)} represents the degree of glucosidation of thealkyl glucosides used according to the invention and is defined as$\overset{\_}{DP} = {{{\frac{p_{1}}{100} \cdot 1} + {\frac{p_{2}}{100} \cdot 2} + {\frac{p_{3}}{100} \cdot 3} + \ldots} = {\Sigma\quad{\frac{p_{i}}{100} \cdot i}}}$

Here, p₁, p₂, p₃ and p_(i) represent the fraction of the mono-, di-,tri- . . . i-fold glucosylated products in percentages by weight.According to the invention, products with degrees of glucosylation from1-2 are chosen advantageously, particularly advantageously from 1.1 to1.5, very particularly advantageously from 1.2-1.4, especially 1.3.

The value DP takes into account the fact that alkyl glucosides generallyrepresent mixtures of mono- and oligoglucosides as a consequence oftheir preparation. According to the invention, a relatively high contentof monoglucosides, typically in the order of magnitude of 40-70% byweight, is advantageous.

Alkyl glycosides used particularly advantageously according to theinvention are chosen from the group consisting of octyl glucopyranoside,nonyl glucopyranoside, decyl glucopyranoside, undecyl glucopyranoside,dodecyl glucopyranoside, tetradecyl glucopyranoside and hexadecylglucopyranoside.

It is likewise advantageous to use natural or synthetic raw materialsand auxiliaries or mixtures which are characterized by an effectivecontent of the active ingredients used according to the invention, forexample Plantaren® 1200 (Henkel KGaA), Oramix® NS 10 (Seppic).

The acyl lactylates are for their part advantageously chosen from thegroup of substances which are characterized by the structural formula

where R¹ is a branched or unbranched alkyl radical having 1 to 30 carbonatoms and M⁺ is chosen from the group of alkali metal ions and the groupof ammonium ions substituted by one or more alkyl radicals and/or one ormore hydroxyalkyl radicals, or corresponds to the half equivalent of analkaline earth metal ion.

For example, sodium isostearyl lactylate, for example the productPathionic® ISL from American Ingredients Company, is advantageous.

The betaines are advantageously chosen from the group of substanceswhich are characterized by the structural formula

where R² is a branched or unbranched alkyl radical having 1 to 30 carbonatoms.

R² is particularly advantageously a branched or unbranched alkyl radicalhaving 6 to 12 carbon atoms.

For example, capramidopropylbetaine, for example the product Tego®Betaine 810 from Th. Goldschmidt AG, is advantageous.

The cocoamphoacetate advantageous according to the invention chosen is,for example, sodium cocoampho-acetate, as is available under the nameMiranol® Ultra C32 from Miranol Chemical Corp.

The preparations according to the invention are advantageouslycharacterized in that the hydrophilic surfactant or surfactants is orare present in concentrations of 0.01-20% by weight, preferably 0.05-10%by weight, particularly preferably 0.1-5% by weight, in each case basedon the total weight of the composition.

For use, the cosmetic and dermatological preparations according to theinvention are applied to the skin and/or the hair in a sufficient amountin the manner customary for cosmetics.

Cosmetic and dermatological preparations according to the invention maybe in various forms. Thus, for example, they may be a solution, ananhydrous preparation, an emulsion or microemulsion of the water-in-oil(W/O) type or of the oil-in-water (O/W) type, a multiple emulsion, forexample of the water-in-oil-in-water (W/O/W) type, a gel, a solid stick,an ointment or else an aerosol. It is also advantageous to administerectoins in encapsulated form, e.g. in collagen matrices and othercustomary encapsulation materials, e.g. as cellulose encapsulations, ingelatin, wax matrices or liposomally encapsulated. In particular, waxmatrices as described in DE-A 43 08 282 have proven to be favorable.Preference is given to emulsions. O/W emulsions are particularlypreferred. Emulsions, W/O emulsions and O/W emulsions are obtainable inthe customary manner.

The emulsifiers used may be, for example, the known W/O and O/Wemulsifiers. It is advantageous to use further customary coemulsifiersin the preferred O/W emulsions according to the invention.

According to the invention, the coemulsifiers chosen are advantageously,for example, O/W emulsifiers, primarily from the group of substanceswith HLB values of 11-16, very particularly advantageously with HLBvalues of 14.5-15.5, provided the O/W emulsifiers have saturatedradicals R and R′. If the O/W emulsifiers have unsaturated radicals Rand/or R′, or if isoalkyl derivatives are present, then the preferredHLB value of such emulsifiers may also be lower or higher.

It is advantageous to choose the fatty alcohol ethoxylates from thegroup of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearylalcohols (cetearyl alcohols). Particular preference is given to:polyethylene glycol(13) stearyl ether (steareth-13), polyethyleneglycol(14) stearyl ether (steareth-14), polyethylene glycol(15) stearylether (steareth-15), polyethylene glycol(16) stearyl ether(steareth-16), polyethylene glycol(17) stearyl ether (steareth-17),polyethylene glycol(18) stearyl ether (steareth-18), polyethyleneglycol(19) stearyl ether (steareth-19), polyethylene glycol(20) stearylether (steareth-20), polyethylene glycol(12) isostearyl ether(isosteareth-12), polyethylene glycol(13) isostearyl ether(isosteareth-13), polyethylene glycol(14) isostearyl ether(isosteareth-14), polyethylene glycol(15) isostearyl ether(isosteareth-15), polyethylene glycol(16) isostearyl ether(isosteareth-16), polyethylene glycol(17) isostearyl ether(isosteareth-17), polyethylene glycol(18) isostearyl ether(isosteareth-18), polyethylene glycol(19) isostearyl ether(isosteareth-19), polyethylene glycol(20) isostearyl ether(isosteareth-20), polyethylene glycol(13) cetyl ether (ceteth-13),polyethylene glycol(14) cetyl ether (ceteth-14), polyethylene glycol(15)cetyl ether (ceteth-15), polyethylene glycol(16) cetyl ether(ceteth-16), polyethylene glycol(17) cetyl ether (ceteth-17),polyethylene glycol(18) cetyl ether (ceteth-18), polyethylene glycol(19)cetyl ether (ceteth-19), polyethylene glycol(20) cetyl ether(ceteth-20), polyethylene glycol(13) isocetyl ether (isoceteth-13),polyethylene glycol(14) isocetyl ether (isoceteth-14), polyethyleneglycol(15) isocetyl ether (isoceteth-15), polyethylene glycol(16)isocetyl ether (isoceteth-16), polyethylene glycol(17) isocetyl ether(isoceteth-17), polyethylene glycol(18) isocetyl ether (isoceteth-18),polyethylene glycol(19) isocetyl ether (isoceteth-19), polyethyleneglycol(20) isocetyl ether (isoceteth-20), polyethylene glycol(12) oleylether (oleth-12), polyethylene glycol(13) oleyl ether (oleth-13),polyethylene glycol(14) oleyl ether (oleth-14), polyethylene glycol(15)oleyl ether (oleth-15), polyethylene glycol(12) lauryl ether(laureth-12), polyethylene glycol(12) isolauryl ether (isolaureth-12),polyethylene glycol(13) cetylstearyl ether (ceteareth-13), polyethyleneglycol(14) cetylstearyl ether (ceteareth-14), polyethylene glycol(15)cetylstearyl ether (ceteareth-15), polyethylene glycol(16) cetylstearylether (ceteareth-16), polyethylene glycol(17) cetylstearyl ether(ceteareth-17), polyethylene glycol(18) cetylstearyl ether(ceteareth-18), polyethylene glycol(19) cetylstearyl ether(ceteareth-19), polyethylene glycol(20) cetylstearyl ether(ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates from thefollowing group:

polyethylene glycol(20) stearate, polyethylene glycol(21) stearate,polyethylene glycol(22) stearate, polyethylene glycol(23) stearate,polyethylene glycol(24) stearate, polyethylene glycol(25) stearate,polyethylene glycol(12) isostearate, polyethylene glycol(13)isostearate, polyethylene glycol(14) isostearate, polyethyleneglycol(15) isostearate, polyethylene glycol(16) isostearate,polyethylene glycol(17) isostearate, polyethylene glycol(18)isostearate, polyethylene glycol(19) isostearate, polyethyleneglycol(20) isostearate, polyethylene glycol(21) isostearate,polyethylene glycol(22) isostearate, polyethylene glycol(23)isostearate, polyethylene glycol(24) isostearate, polyethyleneglycol(25) isostearate, polyethylene glycol(12) oleate, polyethyleneglycol(13) oleate, polyethylene glycol(14) oleate, polyethyleneglycol(15) oleate, polyethylene glycol(16) oleate, polyethyleneglycol(17) oleate, polyethylene glycol(18) oleate, polyethyleneglycol(19) oleate, polyethylene glycol(20) oleate.

Sodium laureth-11 carboxylate can advantageously be used as ethoxylatedalkyl ether carboxylic acid or salt thereof. As alkyl ether sulfate,sodium laureth-14 sulfate can be used advantageously. The ethoxylatedcholesterol derivative used may advantageously be polyethyleneglycol(30) cholesteryl ether. Polyethylene glycol(25) soyasterol hasalso proven useful. Ethoxylated triglycerides which can be usedadvantageously are the polyethylene glycol(60) evening primroseglycerides.

It is also advantageous to choose the polyethylene glycol glycerol fattyacid esters from the group consisting of polyethylene glycol(20)glyceryl laurate, polyethylene glycol(21) glyceryl laurate, polyethyleneglycol(22) glyceryl laurate, polyethylene glycol(23) glyceryl laurate,polyethylene glycol(6) glyceryl caprate/caprinate, polyethyleneglycol(20) glyceryl oleate, polyethylene glycol(20) glycerylisostearate, polyethylene glycol(18) glyceryl oleate (cocoate.

It is likewise favorable to choose the sorbitan esters from the groupconsisting of polyethylene glycol(20) sorbitan monolaurate, polyethyleneglycol(20) sorbitan monostearate, polyethylene glycol(20) sorbitanmonoisostearate, polyethylene glycol(20) sorbitan monopalmitate,polyethylene glycol(20) sorbitan monooleate.

Optional, but according to the invention in some cases advantageous W/Oemulsifiers which may be used are:

fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters ofsaturated and/or unsaturated, branched and/or unbranchedalkanecarboxylic acids of chain length from 8 to 24, in particular12-18, carbon atoms, diglycerol esters of saturated and/or unsaturated,branched and/or unbranched alkane-carboxylic acids of chain length from8 to 24, in particular 12-18, carbon atoms, monoglycerol ethers ofsaturated and/or unsaturated, branched and/or unbranched alcohols ofchain length from 8 to 24, in particular 12-18, carbon atoms, diglycerolethers of saturated and/or unsaturated, branched and/or unbranchedalcohols of chain length from 8 to 24, in particular 12-18, carbonatoms, propylene glycol esters of saturated and/or unsaturated, branchedand/or unbranched alkanecarboxylic acids of chain length from 8 to 24,in particular 12-18, carbon atoms, and sorbitan esters of saturatedand/or unsaturated, branched and/or unbranched alkanecarboxylic acids ofchain length from 8 to 24, in particular 12-18, carbon atoms.

Particularly advantageous W/O emulsifiers are glyceryl monostearate,glyceryl monoisostearate, glyceryl monomyristate, glyceryl monooleate,diglyceryl monostearate, diglyceryl monoisostearate, propylene glycolmonostearate, propylene glycol monoisostearate, propylene glycolmonocaprylate, propylene glycol monolaurate, sorbitan monoisostearate,sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate,sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol,behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol,polyethylene glycol(2) stearyl ether (steareth-2), glyceryl monolaurate,glyceryl monocaprinate, glyceryl monocaprylate.

Preparations preferred according to the invention are particularlysuitable for protecting human skin against aging processes and againstoxidative stress, i.e. against damage by free radicals, as are produced,for example, by solar irradiation, heat and other influences. For this,they are in various administration forms customarily used for thisapplication. Thus, they may in particular be in the form of a lotion oremulsion, such as cream or milk (O/W, W/O, O/W/O, W/O/W), in the form ofoily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, inthe form of solid sticks, or be formulated as aerosol.

The preparation can comprise cosmetic adjuvants which are usedcustomarily in this type of preparation, such as, for example,thickeners, softening agents, moisturizers, surface-active agents,emulsifiers, preservatives, antifoams, perfumes, waxes, lanolin,propellants, dyes and/or pigments which color the composition itself orthe skin, and other ingredients customarily used in cosmetics.

Dispersants and/or solubilizers which may be used are an oil, wax orother fatty substances, a lower mono-alcohol or a lower polyol ormixtures thereof. Particularly preferred monoalcohols or polyols includeethanol, isopropanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment of the invention is an emulsion which is in theform of a protective cream or milk and, apart from the coloring pigmentsaccording to the invention, comprises for example, fatty alcohols, fattyacids, fatty acid esters, in particular triglycerides of fatty acids,lanolin, natural and synthetic oils or waxes and emulsifiers in thepresence of water.

Further preferred embodiments are oily lotions based on natural orsynthetic oils and waxes, lanolin, fatty acid esters, in particulartriglycerides of fatty acids, or oily-alcoholic lotions based on a loweralcohol, such as ethanol, or a glycerol, such as propylene glycol,and/or a polyol, such as glycerol, and oils, waxes and fatty acidesters, such as triglycerides of fatty acids.

The preparation according to the invention can also be in the form of analcoholic gel which comprises one or more lower alcohols or polyols,such as ethanol, propylene glycol or glycerol, and a thickener, such assiliceous earth. The oily-alcoholic gels also comprise natural orsynthetic oil or wax.

The solid sticks consist of natural or synthetic waxes and oils, fattyalcohols, fatty acids, fatty acid esters, lanolin and other fattysubstances.

If a preparation is formulated as an aerosol, the customary propellants,such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generallyused.

The cosmetic preparation can also be used to protect the hair againstphotochemical damage in order to prevent changes in color nuances,decoloring or damage of a mechanical nature. In this case, formulationis suitably in the form of a shampoo, lotion, gel or emulsion forrinsing out, the particular preparation being applied before or aftershampooing, before or after coloring or bleaching or before or after thepermanent wave. A preparation in the form of a lotion or gel for stylingand treatment, in the form of a lotion or gel for brushing or arranginga water wave, in the form of a hair lacquer, permanent wavingcomposition, coloring or bleaching hair composition can also be chosen.

Apart from the coloring pigments according to the invention, thepreparation with photoprotective properties can comprise variousadjuvants used in this type of composition, such as interface-activeagents, thickeners, polymers, softening agents, preservatives, foamstabilizers, electrolytes, organic solvents, silicone derivatives, oils,waxes, antigrease agents, dyes and/or pigments which color thecomposition itself or the hair or other ingredients customarily used forhaircare.

The present invention further provides a method for the production of apreparation which is characterized in that at least one coloring pigmentaccording to the invention is mixed with a cosmetically ordermatologically suitable carrier. The preparations according to theinvention can be produced here using techniques which are well known tothe person skilled in the art.

The present invention will be illustrated by reference to the followingexample.

EXAMPLE

In a 100 ml Erlenmeyer flask, 0.631 g of 2,4,6-tri-amino-2,4,6-triazine(=melamine) was dissolved in 50 ml of deionized water and 0.5 ml oftetramethylammonium hydroxide solution 2.5% strength at 70° C. withstirring, and 0.22 ml of formaldehyde solution 37% strength was added.The clear solution was stirred for 15 minutes in order to ensure theformation of the methylolmelamine. 2 g of Prussian Blue were then addedto the solution. Immediately afterwards, 0.3 ml of H₂O₂ 30% strength wasadded to the now blue suspension to initiate the coating process(polycondensation). The pigment formed was washed by means of acentrifuge using water and acetone, dried and assessed. Compared withthe untreated Prussian Blue, the material coated with melamine exhibitsa significantly more pleasant “greasy-creamy” sensation on the skin.

1. A nonflake coated coloring pigment characterized in that the pigmentconsists of an inorganic or organic, amorphous or partially crystallinematerial which is provided with at least one coating, where each layercomprises at least one cured melamine-formaldehyde resin or consists ofone such resin.
 2. The coloring pigment as claimed in claim 1,characterized in that it consists of iron(III) hexacyanoferrate(II) orchromium(III) oxide.
 3. The coloring pigment as claimed in claim 1,characterized in that the cured melamine-formaldehyde resin comprisesone or more inorganic or organic dyes and/or one or more inorganic ororganic UV absorbers, the dyes being soluble in the medium in which thepigment is coated.
 4. The coloring pigment as claimed in claim 3,characterized in that the dye or the dyes are present in one or moreinside layers comprising melamine-formaldehyde resin and the UV absorberor the UV absorbers are present in one or more outer layers comprisingmelamine-formaldehyde resin.
 5. The coloring pigment as claimed in claim1, characterized in that essentially round cured melamine-formaldehyderesin particles which comprise one or more dyes and/or one or more UVabsorbers or else are free from dyes and/or UV absorbers areadditionally applied to the outermost coating.
 6. The coloring pigmentas claimed in claim 1, characterized in that the curedmelamine-formaldehyde resin of the outermost layer is modified withfunctional groups.
 7. The coloring pigment as claimed in claim 6,characterized in that the functional groups which modify the outermostlayer is introduced via an amino functional compound which has one ormore further functional groups besides the amino group by this aminofunctional compound taking part in the polycondensation reaction betweenmelamine and formaldehyde and is incorporated into themelamine-formaldehyde network via the amino function and where thefunctional groups thus applied to the surface are optionally furthermodified.
 8. The coloring pigment as claimed in claim 6, characterizedin that the cured melamine-formaldehyde resin of the outermost layer ismodified via the methylolamine or amino groups present therein withcompounds reactive to hydroxyl and/or amino groups, withfunctionalization of the surface.
 9. The coloring pigment according toclaim 3, where the dyes present are at least one fluorescent dye and onefurther optionally fluorescent dye in the melamine-formaldehyde resin,where the further dye is present in an amount which imparts essentiallyno color or fluorescence to the pigment when this dye is used on itsown.
 10. A method for the production of a nonflake coloring pigment withone or more coatings, characterized in that in the case of a singlecoating in a first step a coloring pigment is suspended in a basicaqueous medium comprising melamine and formaldehyde and/ormethylolmelamine, which may optionally be alkoxylated, and in a secondstep crosslinking of the organic constituents is brought about bylowering the pH into the acidic range, and in the case of a multiplecoating the steps one and two are repeated with the product of thepreceding coating reaction.
 11. The method as claimed in claim 10,characterized in that some of the melamine is replaced by othercrosslinking molecules from the group consisting of “guanamines, phenolsand ureas” and/or some of the methylolmelamine is replaced bycorresponding guanamine, phenol or urea analogs.
 12. The method asclaimed in claim 10, characterized in that inorganic or organic dyesand/or inorganic or organic UV absorbers are added prior to the onset ofcrosslinking or during crosslinking.
 13. The method as claimed in claim12, characterized in that the dyes added are at least one fluorescentdye and a further optionally fluorescent dye, where the further dye isadded in an amount which imparts essentially no color or fluorescence tothe pigment when this dye is added on its own.
 14. The method as claimedin claim 10, characterized in that the reduction in the pH in the acidicrange is brought about by oxidation of excess formaldehyde and/orunreacted formaldehyde and/or formaldehyde present in themethylolmelamines by means of hydrogen peroxide.
 15. The method asclaimed in claim 10, characterized in that, in the last coating step,besides melamine and formaldehyde and/or methylolmelamine, an aminofunctional compound which has one or more functional groups besides theamino group takes part in the polycondensation reaction, the aminofunctional compound being incorporated into the melamine-formaldehydenetwork via the amino function, and the functional groups thus appliedto the surface optionally being further modified.
 16. The method asclaimed in claim 10, characterized in that the curedmelamine-formaldehyde resin of the outermost layer is reacted via themethylolamine or amino groups present on its surface with compoundswhich have a group which is reactive to hydroxyl and/or amino groups,besides one or more further functional groups.
 17. The use of one ormore of the nonflake coated coloring pigments of claim 1 as effectpigments in cosmetic formulations and/or other products which areintended for application to the skin.
 18. A composition comprising oneor more of the nonflake coated carrier materials of claim 1 as coloringpigment.
 19. The composition as claimed in claim 18 comprising one ormore of the nonflake coated carrier materials of this invention ascoloring pigment, characterized in that the composition is a cosmeticpreparation.